Name: synthesis and testing of supported pt-cu solid solution nanoparticle catalysts for propane dehydrogenation
Uploaded: 2017-07-18T15:00:00
Description: Watch this Scientific Journal Video about Synthesis and Testing of Supported Pt-Cu Solid Solution Nanoparticle Catalysts for Propane Dehydrogenation at JoVE.com

This work was supported by the School of Chemical Engineering, Purdue University. Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM are supported by the Department of Energy and the MRCAT member institutions. The authors also acknowledge the use of beamline 11-ID-C. We thank Evan Wegener for experimental assistance with the XAS.

1. Synthesis of Supported 2 nm Pt-Cu Bimetallic Nanoparticle Catalysts
<ol>
	<li>Preparation of metal precursor solution
	<ol>
		<li>Dissolve 0.125 g of copper nitrate trihydrate (Cu(NO3)2&#183;3H2O) in 1 mL of water to achieve a sky blue solution. 
		Caution: Use protective gloves when handling chemicals.</li>
		<li>Add ammonia dropwise to the copper nitrate solution, forming dark blue precipitates of copper hydroxide. 
		Caution: Use a fume hood for handling...

<ol>
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The Pt-Cu catalysts prepared in this work contain uniform nanoparticles around 2 nm in size, similar to heterogeneous catalysts qualified for industrial application. All the Pt and Cu precursors form bimetallic structures, as opposed to separate monometallic particles. This bimetallic interaction and small particle size are realized by careful control over the synthesis procedures. The impregnation process makes use of the Strong Electrostatic Adsorption (SEA) between metal ions and the surface of certain oxide supports<...

Propane dehydrogenation (PDH) is a key processing step in the production of propylene, taking advantage of shale gas, the fastest growing source of gas in the country1. This reaction breaks two C-H bonds in a propane molecule to form one propylene and molecular hydrogen. Noble metal catalysts, including Pd nanoparticles, exhibit poor selectivity for PDH, breaking the C-C bond to produce methane with a high yield, with the concomitant production of coke, leading to catalyst deactivation. Recent reports showed that selective PDH catalysts could be obtained by the addition of promoters like Zn or In to Pd2,3,4. The promoted catalysts are near 100% selective to PDH, as opposed to less than 50% for monometallic Pd nanoparticles of the same size. The great improvement in selectivity was attributed to the formation of PdZn or PdIn intermetallic compound (IMC) structures on the catalyst surface. The ordered array of two different types of atoms in the IMCs geometrically isolated the Pd active sites with non-catalytic Zn or In atoms, which turned off the side reactions catalyzed by an ensemble (group) of neighboring Pd active sites.
Platinum has the highest intrinsic selectivity among noble metals for propane dehydrogenation, but it is still not satisfactory for commercial use1. Typically, Sn, Zn, In, or Ga is added as promoter for Pt5,6,7,8,9,10,11,12,13. Based on the idea that geometric active site isolation contributes to high selectivity, any non-catalytic element forming an alloy structure with Pt, such as Cu, should also potentially promote catalyst performance14. Several previous studies suggested that the addition of Cu indeed improved the PDH selectivity of Pt catalysts15,16,17,18. Nevertheless, no direct evidence has been reported to determine whether Pt and Cu form bimetallic nanoparticles or ordered structures, which is crucial to understanding the promotional effect of Cu. In the binary phase diagram of Pt-Cu, two different structure types are possible over a wide composition range16,18: intermetallic compound, in which Pt and Cu each occupy specific crystal sites, and solid solution, in which Cu randomly substitutes in the Pt lattice. IMCs form at low temperature and transform into solid solution at around 600 - 800 &#176;C for bulk materials14. This transformation temperature may be lower for nanoparticles, near the reaction temperature of PDH (i.e.&#160;550 &#176;C). Therefore, it is essential to investigate the atomic order of Pt-Cu under reaction conditions. For supported nanoparticles with small particle sizes, it is very challenging to obtain meaningful structural information using laboratory instruments19. The limited repetition of unit cells leads to very broad diffraction peaks with very low intensities. Because of the high fraction of surface atoms in nanoparticles 1 - 3 nm in size, which are oxidized in air, diffraction must be collected in situ using high-flux X-ray, typically available with synchrotron techniques.
The previously reported Pt-Cu PDH catalysts were all larger than 5 nm in size15,16,17,18. However, for noble metal nanoparticle catalysts, there is always a strong desire to maximize catalytic activity per unit cost by synthesizing catalysts with high dispersions (typically around or less than 2 nm in size)19. Though the preparation of bimetallic nanoparticles of this size is possible by standard impregnation methods, rational control over the procedures is necessary. The metal precursors, pH of the impregnating solution, and support type need to be controlled to optimize the anchoring of the metal species onto high-surface area supports. The subsequent calcination and reduction heat treatments should also be carefully controlled to suppress the growth of the metallic nanoparticles.
This article covers the protocol for the synthesis of supported 2 nm Pt-Cu bimetallic nanoparticle catalysts and for the testing of their propane dehydrogenation performance. The structure of the catalysts is investigated by Scanning Transmission Electron Microscopy (STEM), in situ synchrotron X-ray Absorption Spectroscopy (XAS), and in situ synchrotron X-ray diffraction (XRD), which help elucidate the improved catalyst performance upon the introduction of Cu.

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synthesis and testing of supported pt-cu solid solution nanoparticle catalysts for propane dehydrogenation

A convenient method for the synthesis of bimetallic Pt-Cu catalysts and performance tests for propane dehydrogenation and characterization are demonstrated here. The catalyst forms a substitutional solid solution structure, with a small and uniform particle size around 2 nm. This is realized by careful control over the impregnation, calcination, and reduction steps during catalyst preparation and is identified by advanced in situ synchrotron techniques. The catalyst propane dehydrogenation performance continuously improves with increasing Cu:Pt atomic ratio.

The propylene selectivity versus time for Pt and Pt-Cu catalysts measured at an initial propane conversion of about 20% is presented in Figure 1A. Pt catalyst has an initial selectivity of 61%, which increases to about 82% with time on-stream as the catalyst deactivates for 1h. The Pt-0.7Cu catalyst shows a better initial propylene selectivity of 72%. For Pt-2.3Cu and Pt-7.3Cu catalysts, their initial selectivity reach 90% and 96%, respectively, and are maint...

Watch this Scientific Journal Video about Synthesis and Testing of Supported Pt-Cu Solid Solution Nanoparticle Catalysts for Propane Dehydrogenation at JoVE.com

Synthesis and Testing of Supported Pt-Cu Solid Solution Nanoparticle Catalysts for Propane Dehydrogenation

A convenient method for the synthesis of 2 nm supported bimetallic nanoparticle Pt-Cu catalysts for propane dehydrogenation is reported here. In situ synchrotron X-ray techniques allow for the determination of the catalyst structure, which is typically unobtainable using laboratory instruments.

A convenient method for the synthesis of bimetallic Pt-Cu catalysts and performance tests for propane dehydrogenation and characterization are ...

The overall goal of this research is to synthesize new bimetallic catalysts with small uniform particle size and test their performance for alkane dehydrogenation. The goal is to understand the fundamental principles which lead to high olefin selectivity, high rate, long life and thermal stability. This catalyst synthesis method optimizes anchoring of metal species and to support by preparing a solution with a pH that charges the support surface and checks metal ions of opposite charge.Careful control of the calcination and reduction temperatures is needed to achieve small particle size, co-impregnation of the properly chosen metal precursors ensures strong bimetallic interaction which ultimately controls the activity and selectivity. After preparation, we measure the rates, selectivity and stability of the catalysts for alkane dehydrogenation to determine the differences in performance with catalyst composition and correlate these with the structure. First, carefully weight approximately five grams of dry silica on weigh paper and transfer it into a weighing dish.While mixing, add water drop-wise until the silica is completely wet, but with no excess solution. Then, reweigh the wet silica to calculate the amount of water absorbed and to determine the pore volume of the silica support. To prepare the precursor solution, dissolve 0.125 grams of copper nitrate trihydrate in one milliliter of water in a small vile to obtain a sky-blue solution.Add ammonia drop-wise to the copper-nitrate solution forming dark-blue precipitates of copper hydroxide. Continue adding ammonia until the dark-blue precipitates dissolve to form a dark-blue solution and the pH is greater than 10. Next, add 0.198 grams of tetraammineplatinum nitrate to the solution.Then, add water so that the total volume of the solution is 3.5 milliliters which matches the pore volume of five-gram silica support. Heat the solution to 70 degrees Celsius until all the tetraammineplatinum nitrate salts are dissolved. After allowing the dissolved metal precursor solution to cool to room temperature, add a few drops at a time to five grams of silica in a ceramic evaporating dish and stir gently to break up the particles that stick together to achieve a homogeneous distribution of the solution.Dry the impregnated silica-supported catalyst with a copper-to-platinum ratio of 0.7 in an oven at 125 degrees Celsius overnight. On the following day, calcine the cooled catalyst precursor in a furnace at 250 degrees Celsius with a five-degree Celsius permanent ramp rate in air for three hours. Next, transfer the calcined catalyst to a tube furnace for reduction.Place a one-inch layer of quartz wool in the middle of a one-inch quartz tube reactor and load the cooled calcined catalyst into the tube through a plastic funnel. Then, place the tube in a clamshell temperature programmed furnace. After purging the tube with nitrogen for five minutes at room temperature, switch the flow to 5%hydrogen balanced in nitrogen at the same flow rate as nitrogen to reduce the catalyst.Increase the temperature to 150 degrees Celsius with a five-degree Celsius permanent ramp rate and hold for five minutes. Now, start slow-ramping of the temperature at a rate of 2.5 degrees Celsius per minute to 250 degrees Celsius holding the temperature for 15 minutes after every 25-degree-Celsius increase. Ramp to 550 degrees Celsius at 10 degrees Celsius per minute and stay for 30 minutes to complete the reduction.Switch the 5%hydrogen flow back to pure nitrogen to purge the system and cool to room temperature. Then, unload the catalyst and store it in a vial for future use. Place a half-inch layer of quartz wool against the dimple in the middle of a 3/8-inch quartz tube reactor.Next, mix 40 milligrams of silica-supported catalyst precursor with a copper-to-platinum ratio of 0.7 and 960 milligrams of the silica in an empty vial to dilute the catalyst. Using a plastic funnel, load the catalyst mixture into the tube reactor. Wipe the outer wall of both tube ends with lint-free wipes to remove any dirt and to get a good seal with the O-ring.Connect the tube fittings to both ends of the quartz tube reactor and attach them to the reactor system equipped with a clamshell furnace. Following this, turn on the nitrogen flow through the tube reactor. After one minute, close the ball valve on the reactor outlet.After waiting for the system pressure to increase to five pounds per square inch gauge, close the ball valve on the inlet nitrogen line to stop the nitrogen flow and seal the reactor system. After one minute, record the pressure reading from the gauge. Open the ball valve on the reactor outlet to release the pressure before restarting the nitrogen flow by turning on the ball valve on the inlet nitrogen line to purge the system for one minute.Start flowing hydrogen diluted in nitrogen for catalyst reduction before running the reaction and stop the nitrogen flow. Start heating the tube reactor to 550 degrees Celsius with a rate of 10 degrees Celsius. For propane dehydrogenation reaction testing, start the gas chromatograph, or GC, in the reactor system and select the proper method for gas component analysis.Now, switch the reactor gas flow to a bypass line. Flow 100 cubic centimeters per minute of 5%propane and nitrogen diluted in 5%hydrogen diluted in nitrogen. After the propane flow stabilizes, inject the bypass flow into the GC as a reference sample.Next, switch the gas flow back to the reactor tube line to start the reaction and record the time. After the reaction runs for four minutes, inject the reactor outlet gas flow into the GC to get the outlet gas component information. Finally, use the corresponding peak analysis software to analyze each peak.The propylene selectivity versus time for platinum and platinum-copper catalysts is presented here. While the propylene selectivity of the platinum catalysts decreases at higher conversion, the silica-supported catalyst with a copper-to-platinum ratio of 7.3 retains high propylene selectivity at different propane conversions. The catalyst's selectivity increases almost linearly with a copper content in the platinum-copper catalysts.Higher copper content also improves the turnover rates per mole of surface platinum for propane dehydrogenation. There is a close-to-linear relationship between the turnover rate and the catalyst atomic ratio of copper-to-platinum with the carbon balance close to 100%during all reaction tests. The average particle size of the monometallic platinum and platinum-copper catalysts determined by stem imaging are between two and three nanometers.The change of the scattering pattern in the x-ray absorption fine structure spectra of the catalysts with increasing copper-to-platinum ratio suggests the formation of bimetallic nanoparticles with increasing copper content. The XRD pattern of platinum and platinum-copper catalysts showed that their composition differs from the ideal composition of ordered alloys and there is no peak from superlattice diffraction indicating that platinum and copper form a disordered solid solution structure in the catalysts. The diffraction peaks shift to higher angles with increasing copper-to-platinum ratio confirming that the solid solution becomes richer in copper.Once mastered, the impregnation step can be done in about one hour and the consistency like small particles with uniform composition. When preparing metallic alloys by impregnation, it's important to adjust the pH value of the solution and use proper metal complexes according to the type of the support. The solution volume should be equal to the pore volume of the support.After watching this video, you should have a good understanding of how to synthesize supported bimetallic catalysts and test their alkane dehydrogenation performance. This method is broadly applicable and can be used for different catalyst compositions and for many chemical reactions. Don't forget that mixing hydrogen with air in the presence of a metallic catalyst is extremely dangerous and may lead to explosions.You must always purge the reactor with nitrogen before and after hydrogen addition to the catalyst.

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Research

JoVE Journal

Chemistry

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2'-O-thiophenylmethyl Modification and Characterization via Circular Dichroism

Solid-phase synthesis has been used to obtain canonical and modified polymers of nucleic acids, specifically of DNA or RNA, which has made it a popular methodology for applications in various fields and for different research purposes. The procedure described herein focuses on the synthesis, purification, and characterization of dodecamers of RNA 5&#39;-[CUA CGG AAU CAU]-3&#39; containing zero, one, or two modifications located at the C2&#39;-O-position. The probes are based on 2-thiophenylmethyl groups, incorporated into RNA nucleotides via standard organic synthesis and introduced into the corresponding oligonucleotides via their respective phosphoramidites. This report makes use of phosphoramidite chemistry via the four canonical nucleobases (Uridine (U), Cytosine (C), Guanosine (G), Adenosine (A)), as well as 2-thiophenylmethyl functionalized nucleotides modified at the 2&#39;-O-position; however, the methodology is amenable for a large variety of modifications that have been developed over the years. The oligonucleotides were synthesized on a controlled-pore glass (CPG) support followed by cleavage from the resin and deprotection under standard conditions, i.e., a mixture of ammonia and methylamine (AMA) followed by hydrogen fluoride/triethylamine/N-methylpyrrolidinone. The corresponding oligonucleotides were purified via polyacrylamide electrophoresis (20% denaturing) followed by elution, desalting, and isolation via reversed-phase chromatography (Sep-pak, C18-column). Quantification and structural parameters were assessed via ultraviolet-visible (UV-vis) and circular dichroism (CD) photometric analysis, respectively. This report aims to serve as a resource and guide for beginner and expert researchers interested in embarking in this field. It is expected to serve as a work-in-progress as new technologies and methodologies are developed. The description of the methodologies and techniques within this document correspond to a DNA/RNA synthesizer (refurbished and purchased in 2013) that uses phosphoramidite chemistry.

Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2&#039;-O-thiophenylmethyl Modification and Characterization via Circular Dichroism

This article provides a detailed procedure on the solid-phase synthesis, purification, and characterization of dodecamers of RNA modified at the C2&#39;-O-position. UV-vis and circular dichroism photometric analyses are used to quantify and characterize structural aspects, i.e., single-strands or double-strands.

Solid-phase synthesis has been used to obtain canonical and modified polymers of nucleic acids, specifically of DNA or RNA, which has made it a popular ...

Liquid-cell Transmission Electron Microscopy for Tracking Self-assembly of Nanoparticles

Drying a nanoparticle dispersion is a versatile way to create self-assembled structures of nanoparticles, but the mechanism of this process is not fully understood. We have traced the trajectories of individual nanoparticles using liquid-cell transmission electron microscopy (TEM) to investigate the mechanism of the assembly process. Herein, we present the protocols used for liquid-cell TEM studies of the self-assembly mechanism. First, we introduce the detailed synthetic protocols used to produce uniformly sized platinum and lead selenide nanoparticles. Next, we present the microfabrication processes used to produce liquid cells with silicon nitride or silicon windows and then describe the loading and imaging procedures of the liquid-cell TEM technique. Several notes are included to provide helpful tips for the entire process, including how to manage the fragile cell windows. The individual motions of nanoparticles tracked by liquid-cell TEM revealed that changes in the solvent boundaries caused by evaporation affected the self-assembly process of nanoparticles. The solvent boundaries drove nanoparticles to primarily form amorphous aggregates, followed by flattening of the aggregates to produce a 2-dimensional (2D) self-assembled structure. These behaviors are also observed for different nanoparticle types and different liquid-cell compositions.

Here we introduce experimental protocols for the real-time observation of a self-assembly process using liquid-cell transmission electron microscopy.

Drying a nanoparticle dispersion is a versatile way to create self-assembled structures of nanoparticles, but the mechanism of this process is not fully ...

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of NixNb1-xO nanoparticles with different atomic compositions (x = 0.03, 0.08, 0.15, and 0.20) have been prepared by chemical precipitation. These NixNb1-xO catalysts are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The study revealed the sponge-like and fold-like appearance of Ni0.97Nb0.03O and Ni0.92Nb0.08O on the NiO surface, and the larger surface area of these NixNb1-xO catalysts, compared with the bulk NiO. Maximum surface area of 173 m2/g can be obtained for Ni0.92Nb0.08O catalysts. In addition, the catalytic hydroconversion of lignin-derived compounds using the synthesized Ni0.92Nb0.08O catalysts have been investigated.

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

A protocol for the synthesis of sponge-like and fold-like Ni1-xNbxO nanoparticles by chemical precipitation is presented.

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of ...

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity and convenient colorimetric readout. However, high densities of nanoparticles are typically needed for detection. The available synthesis-based enhancement protocols are either limited to gold and silver nanoparticles or rely on precise enzymatic control and optimization. Here, we present a protocol to enhance the colorimetric readout of gold, silver, silica, and iron oxide nanoprobes. It was observed that the colorimetric signal can be improved by up to a 10000-fold factor. The basis for such signal enhancement strategies is the chemical reduction of Au3+ to Au0. There are several chemical reactions that enable the reduction of Au3+ to Au0. In the protocol, Good&#39;s buffers and H2O2 are used and it is possible to favor the deposition of Au0 onto the surface of existing nanoprobes, in detriment of the formation of new gold nanoparticles. The protocol consists of the incubation of the microarray with a solution consisting of chloroauric acid and H2O2 in 2-(N-morpholino)ethanesulfonic acid pH 6 buffer following the nanoprobe-based detection assay. The enhancement solution can be applied to paper and glass-based sensors. Moreover, it can be used in commercially available immunoassays as demonstrated by the application of the method to a commercial allergen microarray. The signal development requires less than 5 min of incubation with the enhancement solution and the readout can be assessed by naked eye or low-end image acquisition devices such as a table-top scanner or a digital camera.

Rapid Nanoprobe Signal Enhancement by In Situ Gold Nanoparticle Synthesis

In this work, a protocol for signal enhancement of nanoprobe-based biosensing is presented. The protocol is based on the reduction of chloroauric acid onto the surface of existing nanoprobes that consist of gold, silver, silica or iron-oxide nanoparticles.

The use of nanoprobes such as gold, silver, silica or iron-oxide nanoparticles as detection reagents in bioanalytical assays can enable high sensitivity ...

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

A rapid, direct solution-based reduction synthesis method to obtain Au, Pd, and Pt aerogels is presented.

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various ...

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

A convenient synthetic route for spirocyclic heterocycles is well sought after due to the molecule&#39;s potential use in biological systems. By means of solid-phase synthesis, regenerating Michael (REM) linker strategies, and 1,3-dipolar cycloaddition, a library of structurally similar heterocycles, both with and without a spirocyclic center, can be constructed. The main advantages of the solid-support synthesis are as follows: first, each reaction step can be driven to completion using a large excess of reagents resulting in high yields; next, the use of commercially available starting materials and reagents keep the costs low; finally, the reaction steps are easy to purify via simple filtration. The REM linker strategy is attractive because of its recyclability and traceless nature. Once a reaction scheme is completed, the linker can be reused multiple times. In a typical solid-phase synthesis, the product contains either a part of or the whole linker, which can prove undesirable. The REM linker is &#34;traceless&#34; and the point of attachment between the product and the polymer is indistinguishable. The high diastereoselectivity of the intramolecular 1,3-dipolar cycloaddition is well documented. Limited by the insolubility of the solid support, the reaction progression can only be monitored by a change in the functional groups (if any) via infrared (IR) spectroscopy. Thus, the structural identification of intermediates cannot be characterized by conventional nuclear magnetic resonance (NMR) spectroscopy. Other limitations to this method stem from the compatibilities of the polymer/linker to the desired chemical reaction scheme. Herein we report a protocol that allows for the convenient production of spirocyclic heterocycles that, with simple modifications, can be automated with high-throughput techniques.

Here we present a protocol to demonstrate an efficient method for the synthesis of spirocyclic heterocycles. The five-step process utilizes solid-phase synthesis and regenerating Michael linker strategies. Generally difficult to synthesize, we present a customizable method for the synthesis of spirocyclic molecules otherwise inaccessible to other modern approaches.

A convenient synthetic route for spirocyclic heterocycles is well sought after due to the molecule&#39;s potential use in biological systems. By means of ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid nanosheets, a series of Pt/xHMNO6/CNTs with different solid acid compositions (x = 5, 20 wt%; M = Nb, Ta; N = Mo, W) have been prepared by carbon nanotube pretreatment, protonic exchange, solid acid exfoliation, aggregation and finally Pt particles impregnation. The Pt/xHMNO6/CNTs are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and NH3-temperature programmed desorption. The study revealed that HNbWO6 nanosheets were attached on CNTs, with some edges of the nanosheets being bent in shape. The acid strength of the supported Pt catalysts increases in the following order: Pt/CNTs &#60; Pt/5HNbWO6/CNTs &#60; Pt/20HNbMoO6/CNTs &#60; Pt/20HNbWO6/CNTs &#60; Pt/20HTaWO6/CNTs. In addition, the catalytic hydroconversion of lignin-derived model compound: diphenyl ether using the synthesized Pt/20HNbWO6 catalyst has been investigated.

A protocol for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs is presented.

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid ...

Synthesis of Aptamer-PEI-g-PEG Modified Gold Nanoparticles Loaded with Doxorubicin for Targeted Drug Delivery

Due to drug resistance and toxicity in healthy cells, use of doxorubicin (DOX) has been limited in clinical cancer therapy. This protocol describes the designing of poly(ethylenimine) grafted with polyethylene glycol (PEI-g-PEG) copolymer functionalized gold nanoparticles (AuNPs) with loaded aptamer (AS1411) and DOX through amide reactions. AS1411 is specifically bonded with targeted nucleolin receptors on cancer cells so that DOX targets cancer cells instead of healthy cells. First, PEG is carboxylated, then grafted to branched PEI to obtain a PEI-g-PEG copolymer, which is confirmed by 1H NMR analysis. Next, PEI-g-PEG copolymer coated gold nanoparticles (PEI-g-PEG@AuNPs) are synthesized, and DOX and AS1411 are covalently bonded to AuNPs gradually via amide reactions. The diameter of the prepared AS1411-g-DOX-g-PEI-g-PEG@AuNPs is ~39.9 nm, with a zeta potential of -29.3 mV, indicating that the nanoparticles are stable in water and cell medium. Cell cytotoxicity assays show that the newly designed DOX loaded AuNPs are able to kill cancer cells (A549). This synthesis demonstrates the delicate arrangement of PEI-g-PEG copolymers, aptamers, and DOX on AuNPs that are achieved by sequential amide reactions. Such aptamer-PEI-g-PEG functionalized AuNPs provide a promising platform for targeted drug delivery in cancer therapy.

In this protocol, doxorubicin-loaded AS1411-g-PEI-g-PEG modified gold nanoparticles are synthesized via three-step amide reactions. Then, doxorubicin is loaded and delivered to target cancer cells for cancer therapy.

Due to drug resistance and toxicity in healthy cells, use of doxorubicin (DOX) has been limited in clinical cancer therapy. This protocol describes the ...